Method of producing combined colored and black and white pictures



Patented Oct. 4, 1938 PATENT UNITED STATES OFFICE,

METHOD OF PRODUCING COMBINED COL- OBED AND BLACK AND WHITE PICTURES Bela Gaspar, Brussels, Belgium No Drawing. Application January I, 1936, Serial No. 57,904, In Germany January 5, 1935 8 Claims.

The present invention relates to a method for the production of an additional black and white or dark metallic silver image in a photographic material in which dyestuffs or dyestuff-forming substances for the formation of the colored image are present in the layer. It has been. found that very good dyestufl pictures combined with, a black and white silver image can be obtained if 36 The special technical advantage of this methodlies in the fact that in the production of the additional silver image it is'not necessary to rely on the selective sensitivity .of the individual or partial layers. This process is particularly suitable for the production of sound films'in which .the dyestufl picture can be combined with a black silver image for emphasizing the deep blacks or shadows.

v A further advantage of this method is that it 8B is possible to produce perfectly clear black and white sound records because the dyestuff may be entirely destroyed in the sound area of the film.

'This process is equally suitable for photographic materials in which the dyestufl-forming 80 substances or the dyestufis are initially present in the layer or in which these substances are brought into the photographic layer after exposure.

Example 1 -A picture isprinted on'an ordinary, light sensitive positive film. The fllmis developed, but not fixed, and is then soaked with a solution, for- A photographic three-color material such, for instance, as is described in my prior British Patents Nos. 408,991'(U. S. Patent No. 1,985,344) or 415,040 (U. S. application Ser. No. 642,960, filed 55 November 16, 1932) and comprising three light A further picsensitive layers 1, II and III colored-,blue-green,

yellow and purple respectively with, for instance, Dis-mine Pure Blue (Schultz 1. c. No. 510), Chrysophenin G (Schultz l. c. No. 726) and Diamine Fast Pink (Ullman, Encyclopadie der Technischen Chemie II Ed. Vol. 3, pg. 647) respectively is taken. Layer I is predominantly sensitized for green and is coated direct on to the support. Layer II is predominantly, sensitized for red and is coated on to the other side 0 of the support and layer 111 is an ordinary blue sensitive silver halide emulsion and is coated on top of layer 11. Three partial images are printed -from positive master images into this material and are developed in the usual way .but not fixed.

The area of the sound record, however, is diffusely exposed in all layers, whereby homogeneous silver deposits are produced in all of the layers. Thedestruction of the dyestuffs is then effected with a solution of an indifferent acid, as, for instance, a 2% solution of hydrobromic acid in which the dyestufl is locally destroyed proportionate to the silver image. Then the metallic silver is re-halogenized, for instance, with:-- i

(a) A solution of 0.25 gm. potassium bichromate and 10 gr. hydrochloric acid per litre of water, orj y (b) Cupric bromide; or

(c) 2 gm. of potassium ferricyanide and 10 gm.

of bromide of potassium in 200 gm. of water.

It is then washed, clarified with sodium bisulphite and dried in the dark. The sound record and, if desired, ablack and white key print,-are then printed from negative master images of the sound record and the key print respectively. Then the film is developed a second time and finally fixed. The result is a three-colorimage with a superimposed black key print and with a black and white sound-record;

For the same purpose a material may also be used'which, in addition to colored layers, also contains a colorless silver halide emulsion layer. Layers which contain .dyestufl-forming 'sub-' stances, as indicated for instance in'U. 8. Patent 4 No. 1,956,017, patented April 24, 1934, or in British Patents Nos. 416,566 (U. 8. Patent No. 2,071,-

first development, the formation or destruction of the dyestui! is performed by such chemical means as do not dissolve the silver halide or do not remove itslight sensitivity, for example, dyestuff formation may be effected by bromic acid and dyestufl' destruction by a 2% sclutionof 'hydrobromic acid. 56

Example 3 Photographic layers which contain the leucoester of vat dyestuffs are exposed and developed and the dyestufi is formed by treatment with a solution containing one per thousand potassium bichromate and one per thousand hydrobromic acid. The silver image is at the same time rehalogenized. The dyestufi image is then clarified by sodium sulphite solution, washed and dried in the dark and then again, as above stated, exposed, developed and fixed. The result is a dyestufi picture which is combined with a black and white image.

I claim:-

1. A method of producing photographic and kinematographic pictures which comprises exposing a light sensitive silver halide layer, developing the latent silver image to form a metallic silver image, incorporating in said layer a color substance selected from the group consisting of dyestuffs and dyestufi-forming substances which may be locally reacted under the influence of said silver image to form a final dyestufi image, treating said layer with an agent which reacts with said silver to form some silver halide and an agent which acts in situ upon said color sub-.

stance to form a dyestuff image, reconverting any remaining silver to light-sensitive silver halide by treatment with an oxidizing agent free of solvents for silver salts and which does not deleteriously afiect said dyestufi image, exposing the rehalogenized layer a second time to produce a latent silver image from the silver halide, developing the last mentioned imageand fixing after this second development.

2. A- method of producing photographic and kinematographic pictures which comprises exposing a light sensitive silver halide emulsion layer containing a dyestuff for the formation of a dyestufi image which may be locally destroyed under the influence of a silver image, developing the latent silver image to form a metallic silver image, treating said layer with a dye-destroying agent which reacts with said silver to form some, silver halide and an agent which acts insitu upon said dyestufi to form a dyestufi image, reconverting any remaining silver to light sensitive silver halide by treatment with an oxidizing agent free of solvents for silver salts and which does not deleteriously affect said dyestuff image, printing an image into the rehalogenized layer containing the dyestufi image, developing the last mentioned image to form a metallic silver image and fixing after the second development.

3. A method of producing photographic and kinematographic pictures, which comprises exposing a multi-layer photographic material ineluding three differently colored and differently sensitized layers containing dyestuffs for the formation of a multi-color' image which dyestuffs may be locally destroyed under the, influence of I a silver'image, developing the latent silver images to form silver images, treating said layer with a dye-destroying.agent which reacts with said silver to form some silver halide and an agent which acts in situ upon said dyestuffs to form dyestuif images, reccnverting any remaining silver to light sensitive silver halide by treatment with an oxidizing agent free of solvents for silver salts and which does not deleteriously affect said dyestuff images, printing an image into the rehalogenized material containing the dyestufi images, developing said last mentioned and black and white photographic and kinemato-.

graphic pictures which comprises exposing a multi-layer material including a plurality of dif ferently colored and differently sensitized layers containing dyestuffs for the production of a multi-color image to positive master images, said dyestuffs being adapted to be locally destroyed under the influence of a silver image, developing the latent silver images to form silver images, destroying the dyestnfis at the points of the silver images by treatment with an agent which reacts with said silver to form some silver halide and an agent which acts in situ upon said dyestufls to form dyestufi images, reconverting any remaining silver to light sensitive silver halide by treatment with an oxidizing agent free of so]- vents for silver salts and which does not deleteriously affect said dyestuii images, exposing the rehalogenized material containing the multicolor image to a negative master image to produce a latent silver image in at least one of the layers, developing the last mentioned latent silver image and fixing after this second development.

5. A method of producing combined colored and black and white photographic and kinematographic pictures which comprises exposing a multi-layer photographic material comprising a plurality of differently sensitized laye'rs containing different dyestufi-forming substances for the production of a multi-color image to positive master images, said dyestuff forming-substances being such as may be reacted under the influence of a silver image to form a dyestuff image, developing the latent silver images to form silver images, converting the dyestuff forming substances at the points free of the silver images into dyestufi images by treatment with an agent which reacts with said silver to form some silver halide and an agent which acts insitu upon said dyestuff forming substances to form dyestuff images, reconverting any remaining silver to light sensitive silver halide by treatment with an oxidizing agent free of solvents for silver salts and which does not deleteriously affect'said dyestuii images, exposing, the rehalogenized material containing the multi-color image to a negative master image to produce a latent silver image in at least one of the layers, developing the last mentioned latent silver image and fixing after this second development.

6. A method of producing colored kinematographic pictures having black and white sound recordsand black and white images which comprises exposing a photographic material including a plurality of silver halide emulsions containing dyestuffs for the production -of a 'multi-color image and selectively sensitized to different spectral ranges, to positive master images of the colored subject, said dyestuffs being adapted-to be locally destroyed under the influence of a silver image, developing the latent silver images to form metallic silver images, producing positive dyestufi images in the emulsions bytreatment with a dye destroying agent which reacts with said silver to form some silver halide and an agent which acts in situ upon said dyestuffs to form dyestuif images, reconverting any remaining silver to light sensitive silver halide by treatment with an oxidizing agent free of solvents for silver salts and which does not deleteriously afiect said dyestufi images, exposing the rehalogenized emulsions containing the dyestu'fi images to a negative master image of the sound record and the black and white subject to produce a image and fixing after this second development.

7. A method of producing photographic and kinematographic pictures from a material in cluding a light sensitive silver halide layer containing a developed'but unfixed metallic silver image and a coloring substance selected from the group consisting of dyestufis and dyestufi forming substances which may be locally reacted under the influence of the silver image, which comprises treating said layer with an agent which reacts withsaid silver to form some silver halide and an agent which acts in situ upon said coloring substance to form a dyestuif image, reconverting any remaining silver to light sensitive silver halide by treatment with an oxidizing agent free of solvents for silver salts and which does not deleteriously afiect said dyestufi image, ex posing the rehalogenized layer a second time to produce a latent silver image, developing the last mentioned image and fixing after the second development.

8. A method of producing photographic and kinematographic pictures from a material including a plurality of diiierently sensitized silver halide layers each of which contains a developed but unflxed metallic silver image and a coloring substance selected from the group consisting ofdyestufis and dyestufi forming substances which 10 may be locally reacted under the influence of the silver image, which comprises treating said layers with an agent which reacts with said silver to form some silver halide and an agent which acts in situ upon said coloring substance to form dyestufl images, reconverting any re maining silver to light sensitive silver halide by treatment with an oxidizing agent free of solvents for silver salts and which does not deleteriously'affect said dyestufi images, exposing the rehalogenized material a second time to produce a latent silver image, developing the last mentioned image and fixing after this second development.

B GASPAR. 

